Field of the Invention
The invention relates to a titanium-containing formulation and a method of preparation of a titanium-containing formulation.
Brief Description of the Background of the Invention Including Prior Art
Titanium plays an important role in the stimulation of plant growth and development. As described by I. PAIS in his publication “The Biological Importance of Titanium” J. Plant Nutr. 6:3-133, 1983, titanium accelerates the biochemical processes, photosynthesis, and plant respiration, and increases the yield by 10-20% while limiting the development of certain diseases caused by fungi. The most preferable form of titanium use in agriculture and horticulture is a titanium complex with ascorbic acid and citric acid, as the resulting complex compounds are well soluble in water, quickly absorbed and non-toxic to plants.
From the description of the Polish patent PL 172871 B1, liquid fertilizer is known containing titanium and microelement salts complexed with ascorbic acid and citric acid. The content of microelements amounts in % by weight: titanium 0.05-0.25, the sum of manganese, molybdenum, zinc, iron 0.2-0.4, and 0.1-0.9 boron. Ascorbic acid and citric acid are introduced in the ratio of 1:(0.02-1).
From the Polish patent application PL 391564 A1, the manner of preparation of a titanium-containing fertilizer is also known, through the reaction of an aqueous solution of ascorbic acid with an alkali metal carbonate and complexing titanium from the aqueous solution of titanium salts. It consists in adding a solution of titanyl sulfate into the aqueous solution of sodium ascorbate and/or potassium having a pH above 9, after the introduction of the preservative in the form of sodium nitrite, and conducting the titanium complexing process until the pH is stabilized at the level of 5.5-6. Then, using additional complexing of titanium and mineral salts contained in the water is conducted through citric acid, and the pH of the formulated product is reduced to the level of 4.7-5.0. The invention also relates to a fertilizer agent, characterized in that it contains 5-10 g/l of titanium in the form of the following complexes: titanium ascorbate and titanium citrate, preferably in the ratio of 85:15, and ca. 0.4% addition of sodium nitrite. In addition, the present invention involves the use of the product as a fertilizer, to be used as crop spraying, in particular on cucumbers, tomatoes and eggplants in the period before and during flowering. The fertilizing agent is administered in the form of a working solution, at a dose of 0.2 l/ha, for vegetables such as tomatoes and cucumbers every 14 days from the moment the rooting of seedlings, and for cereals in three growth phases: tillering, stem elongation and heading. In addition, the agent is suitable for use in admixture with other multicomponent fertilizers, in an amount of 0.01-0.4% in the case of liquid fertilizers and of 0.01-0.05 in the case of crystalline fertilizers.
In turn, from the patent specification PL 163688 B1, the process for preparing the titanium formulation is known, consisting in the preparation of complexes of titanium salt with ascorbic acid, wherein the starting material containing ascorbic acid is introduced into water at 20° C., after which the resulting solution is separated from the environment preferably by adding a small amount of sodium carbonate. To so protected solution, the aqueous solution of titanium salts, preferably of titanyl sulfate is added, and then a small amount of a strong reducing agent, preferably in the form of a solution of titanium trichloride, and the mixture is stirred for 30 minutes. The resulting solution is subjected to neutralization first with a sodium hydroxide solution, and in the final stage with a sodium carbonate solution while maintaining the pH of the solution at a stable level of ca. 3.
The compounds of sodium used in the known solutions of neutralizing the acidic environment, such as sodium carbonate, sodium hydroxide, or mixtures thereof, form sodium sulfate, reacting with the sulfate group derived from the titanyl sulfate and sulfuric acid which stabilize the solution of titanyl sulfate against hydrolysis. This compound (Na2SO4), characterised by low solubility particularly at temperatures near zero degrees Celsius, makes it difficult to store the product at these temperatures, in particular at temperatures below 0° C. The aforesaid problem increases with increasing titanium content in the product, which is the result of using in the production of known formulations of increased amounts of a titanium carrier in the form of titanyl sulfate, which in turn increases the amount of sodium sulfate in the product. An additional disadvantage consists in the fact that with increasing titanium content, the sodium sulfate content in the product makes it impossible to introduce into known titanium formulations of additional plant nutrients, beneficial for the plants, due to the high degree of saturation of the solution.
Surprisingly, it was found that the problems with the low-temperature storage of the titanium formulation with a relatively high content of titanium can be prevented, and at the same time, a stable titanium product can be obtained which is easy to mix with other formulations used in the cultivation and fertilizers, if the sodium compounds, which are used in the known methods to neutralize the acidic environment during the complexing of titanium from titanyl sulfate with ascorbic acid and citric acid, is replaced by other metal compounds, preferably substances which are plant nutrients.
Surprisingly advantageous results were discovered by using magnesium hydroxide (Mg(OH2)) in the present invention to neutralize the acidic environment during titanium complexing with a mixture of ascorbic acid and citric acid, as this allowed the complete removal of sodium from the titanium formulation, while enabling the introduction of magnesium, which is a nutrient necessary for the growth of plants, and the main component of chlorophyll, the green pigment of plants necessary in the process of photosynthesis and the activation of many enzymes.
In this solution, 1 mol of magnesium (24 g) introduced binds one sulfate group (SO4)−2 into magnesium sulfate (MgSO4), while according to the known solutions, the neutralization of one mol of sulfate group into sodium sulfate (Na2SO4) requires introducing two moles of sodium, i.e. 46 g.
It turned out that the use of magnesium in the form of hydroxide unexpectedly allowed obtaining a very stable product, both in low and high temperatures. As shown by the results of physical and chemical tests, the titanium formulation thus obtained is stable in the range from −6 to +45° C. At the same time, the presence of titanium and magnesium in the composition favorably influenced the plant growth.
The essence of the invention consists in that in the known process of titanium complexing with a mixture of ascorbic acid and citric acid, magnesium hydroxide is used to neutralize free sulfate ions, which is at the same time a carrier of magnesium. Moreover, in the process of titanium complexing, acetic acid simultaneously is used as an advantageous preservative which also allows to significantly increase the magnesium content in the titanium formulation.
It also turned out that the presence of magnesium in the form of magnesium acetate in the titanium formulation according to the invention allows to eliminate the agents preventing the development of fungi on the surface of the product during storage which are used in other methods, which can be attributed to the fungicidal properties of acetates.